JPH07188383A - Epoxy resin composition and resin composition for color filter protection film produced by using the composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition containing a novolak epoxy resin, a carboxylic acid-containing resin and a photo-cationic polymerization catalyst, having excellent developability, smoothness, transparency, etc., enabling patterning operation and useful as a protection film for color filter. CONSTITUTION:This composition contains (A) a novolak epoxy resin (e.g. phenol novolak epoxy resin or cresol novolak epoxy resin), (B) a copolymer resin containing (i) an N-substituted maleimide (preferably one or more compounds selected from N-alkyl-substituted maleimide, N-N-cyc loalkyl-substituted maleimide and N-aryl-substituted maleimide) and (ii) (meth)acrylic acid as essential components, (C) a photo-cationic polymerization catalyst and preferably further (D) at least one kind of compound selected from polybasic carboxylic acid anhydride and polybasic carboxylic acid. The amounts of the component B and the component C are preferably 30-300 pts.wt. and 0.01-10wt.% based on 100 pts.wt. of the component A, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition and a color filter protective film resin composition using the same.

[0002]

2. Description of the Related Art A coating film is often formed for the purpose of preventing deterioration and damage of the surface of various articles. In such coating film, a smooth coating film can be obtained, high adhesion to the substrate, toughness, excellent water resistance, chemical resistance, solvent resistance, heat resistance In addition, it is required to have performance such as high light resistance and no deterioration for a long period of time.

In recent years, liquid crystal display devices, solar cells,
As a coating film used for optical disks and the like, applications requiring transparency and the like in addition to the above-mentioned performance are increasing.

For example, in recent years, various color liquid crystal display devices incorporating a color filter have been announced. In the production of this color liquid crystal display element, a color filter is provided on a transparent substrate such as glass, an inorganic thin film made of indium tin oxide (ITO) or the like is vapor-deposited thereon, and a transparent electrode is formed by patterning by a photolithography method. After the formation, a method of disposing liquid crystal on the liquid crystal is becoming mainstream. In this case, the color filter does not have sufficient heat resistance and chemical resistance to withstand the process of depositing ITO on the color filter and forming the transparent electrode by the photolithography method. It is necessary to form a protective film on the color filter.

Properties required of this color filter protective film include heat resistance and chemical resistance, as well as adhesion to a glass substrate or a color filter, coating properties, transparency, and scratch resistance.

Furthermore, in recent years, as the required value of reliability for a liquid crystal display device using a color filter has become higher, a normal protective film is formed on the part of the color filter on the substrate, and unnecessary protection film outside the color filter is formed. A material capable of not forming a protective film is required for the portion.
For example, when the substrates are sealed with each other without interposing a protective film on the portion to be sealed when the cells are assembled by using the sealing material, the adhesion is stronger and higher reliability is obtained.

As a method of forming such a protective film, a method of forming a protective film on a necessary portion by a printing method such as a roll coater and a method of forming a protective film on the entire surface of a substrate with a spinner or the like, and then using a solvent or an alkaline aqueous solution. For example, a method of removing unnecessary portions has been proposed.

However, if an attempt is made to form the protective film by the printing method, not only is the flatness of the color filter insufficient, but there are also problems such as the inclusion of dust. Also,
A method of developing with a solvent or an aqueous alkaline solution is disclosed in, for example, JP-A-3-157407 and JP-A-4-4219.
As described in, for example, Japanese Patent Laid-Open Publication No. 2003-242242, a (meth) acrylic acid ester of an epoxy resin is irradiated with ultraviolet rays using a photopolymerization initiator to form a coating film, which is then treated with an organic solvent such as methylene chloride or an alkaline aqueous solution such as sodium carbonate. A method of dissolving and removing unirradiated portions to obtain a patterned protective film, and further, JP-A-4-153274 and JP-A-4-l64918.
Japanese Patent Laid-Open No. 4-164970, etc., a method for obtaining a patterned protective film using a copolymer of glycidyl methacrylate and a fluorine group-containing ethylenically unsaturated group-containing compound, etc. Is proposed.

However, the protective film obtained by these methods has a drawback that the adhesiveness to a color filter or a glass plate is not always sufficient. When the cause of this was investigated, it was found that the coating film obtained by UV curing of the (meth) acrylic acid ester compound was too brittle and had poor adhesion.

[0010]

Therefore, as a result of diligent efforts, the present inventors have found that the above problems can be solved by combining a novolac epoxy resin, a carboxylic acid-containing resin and a cationic photopolymerization catalyst. I was able to complete the invention.

That is, the object of the present invention is to solve the above-mentioned drawbacks of the conventional materials, and in addition to the characteristics such as heat resistance, chemical resistance, coating property, transparency and scratch resistance, it is particularly excellent in adhesion to the substrate. Another object of the present invention is to provide a patternable epoxy resin composition and a color filter protective film resin composition obtained using the same.

[0012]

The epoxy resin composition of the present invention comprises: Novolac epoxy resin B. (1) N-substituted maleimide, and (2) copolymer resin containing acrylic acid or methacrylic acid as an essential component, and C.I. It contains a photocationic polymerization catalyst. This epoxy resin composition is particularly suitable for a color filter protective film resin composition.

Examples of the novolac epoxy resin as the component A in the present invention include phenol novolac epoxy resin, cresol novolac epoxy resin and bisphenol A novolac epoxy resin. These can be synthesized by epoxidizing a novolak resin such as a phenol novolac resin, a cresol novolac resin or a bisphenol A novolac resin with epichlorohydrin in the presence of a strong alkali such as sodium hydroxide. As the novolac epoxy resin, known ones can be used and can be easily obtained from the market. For example, as phenol novolac epoxy resin, DEN431,438 (Dow Chemical Co., Ltd.)
Manufactured by Yuka Shell Epoxy Co., Ltd., EPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.), and the like, and as cresol novolac epoxy resin, EOCN-102S, 103S, 104.
S, 1020, 1025, 1027 (all manufactured by Nippon Kayaku Co., Ltd.), ESCN195X, 200S, 220 (all manufactured by Sumitomo Chemical Co., Ltd.), etc., and Epiclon N-8 as a bisphenol A novolac epoxy resin.
65,880 (both manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

As the N-substituted maleimide as a monomer component constituting the copolymer resin which is the component B in the present invention, known ones can be used, but N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
N-alkyl group-substituted maleimides such as N-butylmaleimide, N-cycloalkyl group-substituted maleimides such as N-cyclohexylmaleimide, and N-phenylmaleimide and other N
At least one compound selected from the group consisting of aryl group-substituted maleimides can be used. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferable.

Acrylic acid or methacrylic acid, which is a monomer component constituting the copolymer resin as the component B in the present invention, may be used together when used.

The copolymer resin as the component B in the present invention comprises, as monomers constituting the copolymer resin, a copolymerizable unsaturated monomer other than the above-mentioned (1) N-substituted maleimide and (2) acrylic acid or methacrylic acid. It may include a polymer. As such, unsaturated fatty acid ester,
There are aromatic vinyl compounds, N-substituted maleimides, vinyl cyanide compounds and the like.

Examples of the unsaturated fatty acid ester include methyl acrylate, ethyl acrylate, butyl acrylate,
Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, adamantyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, acrylic acid Tricyclo [5.2.1.0 ^2,6 ] decane-3
(Or 4) -ylmethyl, bornyl acrylate, isobornyl acrylate, methylcyclohexyl acrylate, etc. Acrylic acid cycloalkyl ester having a C 7-20 alicyclic hydrocarbon group containing a tertiary carbon in the ring, acrylic acid Acrylic acid cycloalkyl esters other than those mentioned above such as cyclohexyl, acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, acrylic acid 2-
Acrylic esters such as hydroxyethyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Methacrylic acid alkyl ester such as 2-ethylhexyl methacrylate, norbornyl methacrylate, norbornyl methyl methacrylate, adamantyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-
8-yl, tricyclomethacrylate [5.2.1.0
Methacryl having a C7-20 alicyclic hydrocarbon group containing a tertiary carbon in the ring, such as ^2,6 ] decane-3 (or 4) -ylmethyl, bornyl methacrylate, isobornyl methacrylate, and methylcyclohexyl methacrylate. Acid cycloalkyl ester, cycloalkyl methacrylate other than the above such as cyclohexyl methacrylate, methacrylic acid aromatic ester such as phenyl methacrylate and benzyl methacrylate, and methacrylic acid ester such as 2-hydroxyethyl methacrylate.

Examples of the aromatic vinyl compound include styrene or α-substituted styrene such as α-methylstyrene and α-ethylstyrene, chlorostyrene, vinyltoluene,
Nuclear substituted styrenes such as t-butylstyrene are available.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

The above-mentioned respective monomers are (1) 20 to 70% by weight of N-substituted maleimide, (2) 5 to 30% by weight of acrylic acid or methacrylic acid, and (3) based on the total amount thereof. Other copolymerizable unsaturated monomer components 0
It is preferable to use 100% by weight as a whole in a ratio within the range of 50% by weight. If the amount of component (1) is too large, the adhesion of the resulting coating film tends to decrease, and if it is too small, the heat resistance and coatability tend to decrease. (2)
If the amount of the component is too small, the heat resistance and scratch resistance of the obtained coating film tend to be lowered, and if it is too large, the chemical resistance and coatability of the coating film tend to be lowered. (3) If the amount of other copolymerizable unsaturated monomer is too much, the effect of the present invention tends to be insufficient.

The copolymer resin as the component B is prepared by blending the monomers (1), (2) and (3) another copolymerizable unsaturated monomer component and copolymerizing them. It can be manufactured. Known methods such as radical polymerization and ionic polymerization can be used. For example, it can be produced by a method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method in the presence of a polymerization initiator.

Examples of the above-mentioned polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate and t-butylperoxy-2.
-Ethyl hexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and other organic peroxides, azobisisobutyronitrile, azobis-
Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl, water-soluble catalysts represented by potassium persulfate and ammonium persulfate, and peroxides or persulfates. Any redox catalyst that can be used in ordinary radical polymerization, such as a redox catalyst obtained by combining a solvent and a reducing agent, can be used. The polymerization catalyst is preferably used in the range of 0.01 to 10% by weight based on the total amount of the above monomers.

Further, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer and the like can be added as a polymerization regulator as necessary for controlling the molecular weight.

The polymerization temperature is preferably selected in the range of 0 to 200 ° C, particularly preferably 50 to 120 ° C.

As the solvent in the solution polymerization, the solvent used in ordinary radical polymerization can be used. Specific examples include aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ether solvents such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; ethyl acetate, acetic acid-
n-propyl, isopropyl acetate, -n-butyl acetate,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Examples include ester solvents such as γ-butyrolactone; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these solvents,
Ester solvent and ketone solvent are preferred, alone,
Alternatively, two or more kinds can be mixed and used.
In addition, usually, when used as a coating resin composition, since it contains a solvent, it is preferable to polymerize by a solution polymerization method using the same solvent, but the polymer is prepared by a method such as methanol reprecipitation method after polymer production. It is also possible to isolate and dissolve in another solvent before use.

As the photocationic polymerization catalyst which is the C component in the present invention, any conventionally known photocationic polymerization catalyst can be used. For example, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt and the like can be mentioned. As diallyl iodonium salt,
Diphenyliodonium hexafluorophosphate,
Examples thereof include diphenyliodonium hexafluoroantimonate, di (4-methoxyphenyl) iodonium chloride, and (4-methylphenyl) phenyliodonium. Examples of the triallylsulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroborate and the like. Examples of the triallyl selenium salt include triphenyl selenium hexafluorophosphate and triphenyl selenium hexafluoroantimonate.

Further, these photocationic polymerization catalysts can be easily put on the market. For example, SP-
170, SP-150 (all manufactured by Asahi Denka Co., Ltd.,
Polyarylsulfonium hexafluorophosphate, polyarylsulfonium hexafluoroantimonate), UVE-1014 (manufactured by General Electric Company, polyarylsulfonium hexafluoroantimonate salt), FC-508, FX-512
(Manufactured by 3M Company, polyarylsulfonium hexafluorophosphate) and the like. These cationic photopolymerization catalysts can be used alone or in combination of two or more at an arbitrary ratio.

The epoxy resin composition of the present invention includes
If necessary, various components (component D) may be used in addition to the components A to C. It is preferable to use at least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the D component,
It is preferable from the viewpoint of improving chemical resistance.

Examples of the polyvalent carboxylic acid anhydrides include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride,
Aliphatic dicarboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride and methylendomethylenetetrahydrophthalic anhydride; Fats such as cyclopentanetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Group polycarboxylic acid dianhydrides; aromatics such as phthalic anhydride, trimetic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Polyhydric carboxylic acid anhydrides; ester group-containing acid anhydrides such as ethylene glycol bis trimellitate and glycerin tris trimellitate can be mentioned. Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid and cyclopentanetetracarboxylic acid; phthalic acid. Acid, terephthalic acid, isophthalic acid, trimellitic acid,
Examples thereof include aromatic polyvalent carboxylic acids such as pyromellitic acid and benzophenonetetracarboxylic acid.

The polyvalent carboxylic acid anhydride and polyvalent carboxylic acid may be used alone or in combination of two or more. From the viewpoint of heat resistance, aromatic polycarboxylic acid anhydrides and aromatic polycarboxylic acids are preferable from the viewpoint of heat resistance, and trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in solvents.

In the epoxy resin composition of the present invention, it is preferable to add 30 to 300 parts by weight of the copolymer resin of component B to 100 parts by weight of the epoxy resin of component A. If the amount of the component B copolymer resin is too small, the adhesion tends to decrease, and if it is too large, the chemical resistance tends to decrease. The cationic photopolymerization catalyst as the component C is preferably used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the epoxy resin of the component A. If the amount of C component is too small, the exposed portion tends to be insufficiently cured, and if it is too large, the coating film tends to be colored. At least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids as the D component is 0 to 100 parts by weight of the B component copolymer resin.
It is preferable to use 50 parts by weight. If polycarboxylic acid anhydride or polycarboxylic acid is too much, coating property,
The chemical resistance tends to decrease. The polycarboxylic acid anhydride or polycarboxylic acid is preferably used in an amount of 5 parts by weight or more in order to exert the effect of its use.

A coupling agent may be added to the epoxy resin composition of the present invention in order to improve its adhesion. As the coupling agent, a functional silane coupling agent is preferably a vinyl group,
A silane coupling agent having a reactive substituent such as a methacryloyl group, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, an epoxy group, specifically vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxy. Examples thereof include silane, γ-isocyanatopropyltriethoxysilica, and γ-glycidoxypropyltrimethoxysilane. Particularly, a silane coupling agent having an epoxy group is preferable because it has excellent adhesiveness and solvent resistance. These functional silane coupling agents may be used alone or in combination of two or more. The amount of the functional silane coupling agent used is preferably in the range of 0 to 10 parts by weight when the total amount of the epoxy resin as the component A and the copolymer resin as the component B is 100 parts by weight. If it is too much, the chemical resistance tends to decrease. Further, in order to exert the effect of use, it is preferable to use 0.1 part by weight or more.

The epoxy resin composition of the present invention can be usually dissolved in a solvent, applied, and cured by heating to form a coating film. The solvent is not particularly limited as long as it dissolves the above composition and does not react with these components. Specific examples thereof include the solvents exemplified as the solvent for solution polymerization of the copolymer resin which is the component A of the present invention. Of these solvents, ester solvents and ketone solvents are preferable, and they can be used alone or in admixture of two or more.

The method of preparing the composition solution by dissolving the epoxy resin composition in the present invention in a solvent is not particularly limited, and even if the composition solution is prepared by simultaneously dissolving all the components in the solvent. Well, if necessary, each component may be appropriately made into two or more solutions, and these may be mixed at the time of use to form a composition solution. When the composition solution is prepared as described above, the amount of the solvent used is preferably 50 to 95% by weight of the total amount of the final composition solution used for coating. If it is less than 50% by weight, the solid content concentration is too high, and the leveling property of the coating film may be lowered, or the transparency of the coating film may be reduced, while if it exceeds 95% by weight, the solid content concentration is too low. Therefore, the chemical resistance of the coating film may be insufficient. Further, in the above composition, if necessary, an epibis type, alicyclic epoxy resin, a carboxyl group-containing polymer compound, a curing accelerator used for curing the epoxy resin, an antioxidant, an ultraviolet absorber, or the like. Stabilizers and the like may be added.

The method of applying the solution of the epoxy resin composition according to the present invention is not particularly limited, and in addition to the dipping method, the spray method, the roll coating method, the spin coating method and the like, a coating method by printing such as screen printing and offset printing. There are laws etc.
The heat curing conditions for the above composition are appropriately selected depending on the specific type of each component of the composition, the compounding ratio, etc.
It is about 5 to 30 minutes at about 90 ° C. After heating and curing, for example, ultraviolet rays are radiated through a mask having a predetermined pattern, and then development is performed using a developing solution to remove unnecessary portions to form a pattern.

Examples of the developer include alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, ethylamine, diethylamine, triethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide. Aqueous solution or methylene chloride, chlorocene, acetone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, γ-butyroctone, dimethylformamide, Use an organic solvent such as dimethylacetamide or N-methylpyrrolidone. It can be.

The developing time in the previous development is usually 3
The developing time may be 0 to 300 seconds, and any conventionally known method such as a diving method may be used. When developing with an alkaline aqueous solution, washing with running water is usually carried out for about 30 to 60 seconds and then dried.
Further, when the development is performed with an organic solvent, it can be dried as it is. In any case, 150 to 3
By performing heat treatment in the range of 00 ° C. for 0.5 to 2 hours, a protective film having excellent heat resistance, solvent resistance, hardness and the like can be obtained.

The coating film formed of the epoxy resin composition of the present invention exhibits excellent adhesion to various materials such as glass, metal and plastic, and is smooth and smooth.
Since it is tough and has excellent light resistance, heat resistance, water resistance, solvent resistance, and transparency, it is useful as a coating film for various articles. In particular, as a color filter protective film, a surface protective layer or a dye protective layer of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resin with a dye or coloring by dispersing a pigment. Is useful as When used as a color filter protective film, the film thickness after heat curing is 0.005 to
It can be appropriately applied and used so as to have a thickness of about 30 μm, preferably about 0.1 to 10 μm.

In the prior art, no patterning is possible and all the required properties such as coating property, adhesiveness and heat resistance are satisfied. However, the epoxy resin composition of the present invention contains a compound having a specific structure. By combining them, these required characteristics can be satisfied in a well-balanced manner.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (Production of Copolymer Resin Solution B-1) 150 parts by weight of cellosolve acetate (acetoxyethoxyethane) in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introducing tube, reflux condenser and dropping funnel. The inside of the charged flask was replaced with nitrogen. N-phenylmaleimide 14
0 parts by weight, 40 parts by weight of methacrylic acid, 20 parts by weight of methyl acrylate and 3.0 parts by weight of azobisisobutyronitrile were dissolved in 300 parts by weight of cellosolve acetate, and the above-mentioned 1 liter flask was heated at 90 ° C. in a nitrogen stream. It was added dropwise over 3 hours. After further stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 16.7 parts by weight of cellosolve acetate was added, and then the temperature was raised to 120 ° C. and maintained for 2 hours. The viscosity of the obtained copolymer resin solution was 560 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 22,000. The weight average molecular weight was measured by HLC analysis. The analysis conditions were GPC mode, using a gel pack A-120 + gel pack A-140 + gel pack A-150 (all are trade names of Hitachi Chemical Co., Ltd.) as a column, tetrahydrofuran as an eluent, and a differential refractometer as a detector.

Production Example 2 (Production of Copolymer Resin Solution B-2) Except that in Production Example 1, the monomers used were N-cyclomaleimide 120 parts by weight, methacrylic acid 40 parts by weight, and methyl methacrylate 40 parts by weight. Was carried out according to Production Example 1. The viscosity of the obtained copolymer resin solution was 480 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 20,000.
Met.

Production Example 3 (Production of Copolymer Resin Solution B-3) In Production Example 1, the monomers used were 100 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid and tricyclomethacrylate [5.2.1. 0 ^2,6 ] decane-8
-Ill was carried out in accordance with Production Example 1 except that the amount was 60 parts by weight. The viscosity of the obtained copolymer resin solution was 350 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 12,000.

Examples 1 to 6 Phenol novolac epoxy resin (DEN-431, Dow Chemical Co., Ltd. trade name) or cresol novolac epoxy resin (EO) as component A in the present invention
CN-103S, trade name of Nippon Kayaku Co., Ltd.) 100 parts by weight, 667 parts by weight of any of the copolymer resin solutions B-1 to 3 obtained in Production Examples 1 to 3 as component B, trimellitic anhydride 30 Parts by weight, γ-glycidoxypropyltrimethoxysilane [SH-6040; Toray Dow Corning
3.3 parts by weight of Silicone Co., Ltd.], 457 parts by weight of cellosolve acetate, and 396 parts by weight of diethylene glycol dimethyl ether were added and uniformly mixed and dissolved at room temperature. Table 1 shows combinations of the components A and B.

This solution was filtered with a membrane filter having a pore size of 0.2 μm, and then spin-coated on a glass plate (Dow Corning 7059 material, non-alkali glass) using a spin coater at a rotation speed of 1,000 rpm. After coating, heat the glass plate in a constant temperature bath at 160 ° C for 1 hour,
The coating was cured. The surface of the obtained coating film was extremely smooth, and pinholes and the like were not observed at all. The film thickness measured by a stylus type film thickness meter [Surfcom; trade name of Tokyo Seimitsu Co., Ltd.] was 1.3 to 1.6 μm. Then, directly contact a predetermined negative film on this coating film,
Ultraviolet irradiation was performed using a 5 KW ultra-high pressure mercury lamp. The unirradiated portion was dissolved and removed with methylene chloride, or dissolved and removed with a 1% sodium hydroxide aqueous solution and rinsed with ultrapure water for 1 minute, and the developability was good. In addition, the criterion for developing property is that the dissolution rate of the unirradiated area is fast and the irradiated area is clearly left, ○, the dissolution rate of the unirradiated area is slow, or it does not dissolve, or conversely The thing which melt | dissolved to a part was set as x. After development 1
The coating film was heat-cured for 1 hour in a constant temperature bath of 80 ° C. The surface of the obtained coating film was extremely smooth, and pinholes and the like were not observed at all.

The following tests were conducted on the coating films thus produced. In order to check the adhesion of the coating film to the glass plate, a tape-like test by tape peeling (JIS-K-54
00) was performed. As a result, the remaining number was 100/100, and peeling was not observed at all.

Next, when the same glass plate as the one coated with the absorption spectrum at 400 nm to 800 nm of the coating film was measured as a reference, the light transmittance was 95% or more in the entire region.

Further, the glass plate with this coating film was subjected to a pressure cooker test (120 ° C., 2 atm) for 30 hours (hereinafter referred to as PCT treatment), and immersed in N-methylpyrrolidone at room temperature for 30 minutes (hereinafter referred to as NMP treatment). 5%)
Aqueous sodium hydroxide solution (hereinafter referred to as NaOH treatment)
Soak for 30 minutes at room temperature in a oven at 280 ° C for 1
The treatments that were left for a time (hereinafter referred to as 280 ° C. treatment) were separately performed, and after each treatment, the above-mentioned goggles test and the measurement of the light transmittance were performed. When these results were compared with the test results immediately after coating film production (immediately after curing), adhesiveness and light transmittance were good in all cases. The results of the developability test are shown in Table 2, the results of the goose eye test are shown in Table 3, and the results of the light transmittance test are shown in Table 4.

Comparative Example 1 Cresol novolac epoxy resin (EOCN-103)
S, Nippon Kayaku Co., Ltd. product name) 100 parts by weight, trimellitic anhydride 30 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd., SH-6040) 1.0 Parts by weight, SP-15
0 (manufactured by Asahi Denka Co., Ltd.) and 400 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, and the obtained solution was applied on a glass plate and cured by heating in the same manner as in the example. Then, various characteristics tests of the coating film were conducted. The developability test results are shown in Table 2, the goose eye test results are shown in Table 3, and the light transmittance test results are shown in Table 4.

Comparative Example 2 100 parts by weight of glycidyl polymethacrylate (weight average molecular weight in terms of standard polystyrene: about 80,000), 10 parts by weight of trimellitic anhydride, γ-glycidoxypropyltrimethoxysilane [SH-6040; Toray・ Dow Corning Silicone Co., Ltd. product name] 1.0 part by weight, SP-
150 parts by weight of Asahi Denka Kogyo Co., Ltd. and 580 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature,
The obtained solution was applied onto glass and heat-cured in the same manner as in Examples, and various characteristics tests of coating films were conducted. The developability test results are shown in Table 2, the goose eye test results are shown in Table 3, and the light transmittance test results are shown in Table 4.

[0051]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Combination of A component and B component ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ A component: epoxy resin Copolymer resin B ───────── ─────────────────────────── Example 1 DEN-431 B-1 Example 2 DEN-431 B-2 Example 3 DEN- 431 B-3 Example 4 EOCN-102S B-1 Example 5 EOCN-102S B-2 Example 6 EOCN-102S B-3 ━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━

[0052]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Developability test results ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Current image liquid Methylene chloride 1% sodium hydroxide ─────────── ───────────────────────── Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ○ ○ Example 6 ○ ○ Comparative Example 1 × × Comparative Example 2 × × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0053]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 3 Gobang eye test results (remaining number / 100 ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ° C. After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 100/100 100/100 100/100 100 / 100 100/100 Example 2 100/100 100/100 100/100 100/100 100/100 Example 3 100/100 100/100 100/100 100/100 100/100 Example 4 100/100 100/100 100 / 100 100/100 100/100 Example 5 100/100 100/100 100/100 100/100 100/100 Example 6 100/100 100/100 100/100 100/100 100/100 Comparative Example 1 100/100 0/100 100/100 100/100 100/100 Comparative example 2 100/100 0/100 100/100 0/100 100/100 ━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━ ━━━━

[0054]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 4 Light transmittance test results (400 to 800 nm ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ° C. After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 95% or more 95% or more 95% or more 95% 90% or more Example 2 95% or more 95% or more 95% or more 95% or more 90% Example 3 95% or more 95% or more 95% or more 95% or more 90% Example 4 95% or more 95% or more 95% or more 95 % Or more 90% Example 5 95% or more 95% or more 95% or more 95% or more 90% Example 6 95% or more 95% or more 95% or more 95% or more 90% Comparative Example 1 95% or more 95% or more 95% or more 80% 70% Comparative Example 2 95% or more and 50% or less 80% 50% or less 95% or more ━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━

Test Example The composition solutions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were used to examine suitability for a color filter substrate. As a test method, a color filter substrate was prepared by a generally known method, and the coating property and heat resistance on this substrate were examined.
The color filter substrate is prepared by first gelatin-ammonium dichromate (10: 1, weight ratio) on a transparent glass substrate.
After spin-coating the aqueous solution of to give a film thickness after drying of 1 μm, it is dried at 80 ° C. for 10 minutes, the resulting coating film is irradiated with ultraviolet rays and then developed with pure water to give a dyed substrate layer. Got This was immersed in a red dye bath having the following composition, washed with water, and dried at 150 ° C. for 30 minutes to form a color filter substrate dyed red. Composition of dyeing bath Suminol Milling Red RS (Sumitomo Chemical Co., Ltd.) 2g Acetic acid 3g Distilled water 100g

Next, the composition solution was spin-coated at 800 rpm on the color filter substrate and dried at 80 ° C. for 10 minutes on a hot plate to give a thickness of 1.3 to
A 1.6 μm coating film was formed. Thereafter, a predetermined negative film was brought into direct contact with the film, and UV irradiation was performed using a 5 KW ultra-high pressure mercury lamp. Next, the non-irradiated portion outside the color filter was dissolved and removed with a 1% aqueous sodium hydroxide solution, and washed with ultrapure water for 1 minute. Further, a protective layer was formed by treating in a constant temperature bath at 180 ° C. for 1 hour.

Indium tin oxide (ITO) was vapor-deposited on the thus-prepared color filter with a protective film by a conventional method, and then patterned by photolithography. The color filter having the ITO pattern was observed in detail with an optical microscope.
No wrinkles or cracks were observed on the color filter or the protective film produced using the composition of No. 6, and the adhesiveness and adhesion between the color filter and the protective film were good as shown in Table 5.

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[Table 5] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 5 Color filter substrate proper test results ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Composition Color filter after ITO deposition Adhesion with surface condition ─── ──────────────────────────────── Example 1 〇 〇 Example 2 〇 〇 Example 3 〇 〇 Example 1 〇 〇 Example 2 〇 〇 Example 3 〇 〇 Comparative Example 1 〇 × Comparative Example 2 × × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━ In Table 5, the surface condition after ITO vapor deposition is ◯ when there is no abnormality, x when there are wrinkles and cracks, and the adhesion with the color filter is a goggles test. Those that did not come off 〇, completely Was × things but the.

[0059]

EFFECTS OF THE INVENTION In the epoxy resin composition according to claims 1 to 3, the coating film formed from the composition is capable of patterning, has excellent developability, and has smoothness, transparency, adhesiveness, and moisture resistance. Excellent in chemical resistance, heat resistance and scratch resistance. The color filter protective film resin composition according to claim 4 contains the epoxy resin composition according to any one of claims 1 to 3, is useful as a color filter protective film, and is similar to the resin composition. Have an effect.

Claims (4)

[Claims] 1. A. Novolac epoxy resin B. (1) N-substituted maleimide, and (2) copolymer resin containing acrylic acid or methacrylic acid as an essential component, and C.I. An epoxy resin composition containing a photocationic polymerization catalyst. 2. The D.I. At least 1 selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids
The epoxy resin composition according to claim 1, which contains one kind of compound. 3. The N-substituted maleimide is at least one compound selected from the group consisting of N-alkyl group-substituted maleimides, NN-cycloalkyl group-substituted maleimides, and N-aryl group-substituted maleimides. The epoxy resin composition according to claim 2. 4. A resin composition for a color filter protective film, which comprises the epoxy resin composition according to claim 1, claim 2, or claim 3.